DE665476C - Process for the preparation of amide-like condensation products of aromatic sulfonic acids - Google Patents

Description

GERMAN EMPIRE

ISSUED ON SEPTEMBER 29, 1938

REICH PATENT OFFICE

PATENT LETTERING

M 665476 CLASS 12 ο GROUP 23 oi

Patented in the German Empire on October 6, 1935

It has been found that valuable amide-like condensation products of aromatic sulfonic acids are obtained in a simple manner if aromatic disulfonic or dicarboxylic acid chlorides, aliphatic dicarboxylic acid chlorides or phosgene are used on both sides in aqueous solution with neutralized sulfonic acid group-containing aminoarylacidylamidoaryl compounds (CO ₂ = —SO 2 - and / or —CO2 - ■), which still contain an acidylatable amino group, reacts, in the reaction products about \ existing nitro groups or non-aromatically acylated amino groups are reduced or exposed and the free amino groups thus formed are acylated in aqueous solution with neutralized arylsulfonic or carboxylic acid chlorides, the reaction components so be chosen so that the resulting products contain at least four sulfimido groups and at least two sulfonic acid groups. In this way, polyarylsulfamidoaryl derivatives with a linear structure and containing at least five aromatic nuclei are formed.

Of disulfonic or dicarboxylic acids, the halides of which are suitable for the process, are for example those of the benzene, diphenyl and naphthalene series, such as about benzene disulphonic acids, toluene disulphonic acids, naphthalene-1 · 5- or -2 · 6-disulphonic acid, Diphenylsulfonedisulfonic acid, phthalic acid, isophthalic acid, oxalic acid and the like. Those containing sulfonic acid groups used for condensation SuIf- or carboxylic acid amidoaryl compounds which have an acidylatable Must contain amino group can be used alone or in admixture with one another will. In addition to other substituents, they can also have nitro groups or non-aromatic groups contain acylated amino groups. In these cases the nitro groups are reduced or acylamino groups are saponified and the free amino groups formed in this way, for example by reaction with aromatic ones Sulfonic or carboxylic acid chlorides further acylated, the chlorides used for the final condensation expediently in m- or in m- and p-positions to the acid chloride group by suitable substituents, in particular halogen, are substituted.

The condensation of the acid halides with the amino compounds takes place according to known methods Methods, advantageously in an aqueous medium, in the presence of acid-forming agents.

Dissolve the alkali and ammonium salts of the condensation products obtainable in this way

Von dein Patt'iitsiiclier has given as the inventor:

Dr. Johann Hu is in Leverkusen-Wiesdorf.

in water to form more or less viscous solutions which, after weak acidification, are excellent tanning extracts; ? they provide from tanning in the usual '", a beautiful white and especially s $ ^jfif. lightfast leather In addition, the Pi ^-products as a reservation agent for TIE ⁴ generic fiber to staining by substantive dyes and as a precipitant

ίο for basic dyes in paint dyeing be used. Before the known condensation products of aromatic diamines with aromatic sulfonic acid or carboxylic acid chlorides the new products are characterized by the fact that they usually have a reduced sensitivity to salt and a have higher lightfastness.

Unless otherwise stated, the quantities given in the examples below relate noted, on parts by weight.

Example ι

483 parts of 3 "-aminobenzene-i" -sulfonyl 3'-aminobenzene-i'-sulfonylaniline-4-sulfonic acid (produced by condensation of aniline-4-sulfonic acid sodium in aqueous solution with 2-nitrobenzene-4-sulfochloride in the presence of chalk and reduction of the condensation product with iron flour, further condensation of the amino compound obtained with the necessary amount of 2-nitrobenzenesulfochloride and further iron reduction) are brought into solution in about 3400 parts of water and the equivalent amount of sodium hydroxide solution. The well stirring the solution at about 40 ⁰ with 80 parts of chalk and 215 parts of a 1 × 2-dichlorobenzene-4 · 6-disulfochlorids from F. IIQ to set into ^0, which is obtained by boiling for several hours of ι · 2-dichlorobenzene at about iof the amount by weight of chlorosulfonic acid, discharging the cooled sulfonation mixture

Can win pure ice and dissolving the precipitated and dried disulfochloride from benzene. Expediently, the disulfochloride is / are siphoned off before the reaction and ground with cold water to form a fine paste. The mixture is left for about 12 hours at 40 ⁰ mull, the temperature increases gradually for several hours to 60 to 70 ⁰ and closing-Hch at 90 to 95 ⁰ wherein one another by possibly adding chalk amounts ensures that the reaction neutral remain.' If a sample taken from the condensation mixture no longer absorbs nitrite, the broth is made clearly mineral acid with crude hydrochloric acid and the reaction product is salted in the heat using a conc. Calcium chloride solution. The product separates out in oily form and solidifies when the mixture cools to form a viscous, light-colored syrup, from which the aqueous broth is removed as far as possible by pouring it off and pressing it off.

To purify and convert the sodium-lime-salt mixture into a lime salt that is as uniform as possible, the condensation product is dissolved 2 to 3 times with 2000 parts of water each time at about 60 °, with conc. Calcium chloride solution is precipitated again and the alkalis are removed in the cold by pouring and pressing. Finally, the viscous syrup obtained is dissolved in about 1000 parts of warm water and, at 60 to yes °, the calcium salt of the condensation product is converted into the corresponding ammonium salt by adding the necessary amount of ammonium oxalate to the well-stirred solution. The pale yellow syrup sucked off by the excreted calcium oxalate in the heat contains small amounts of chlorammonium and mainly the condensation product of the composition

SO »- NH-

'-SO, H

SO., - NH- /

Cl- /
Cl

SO., - NH- <SOo-NH-

, - HO> S

The dry substance obtained by evaporating the syrup is a light yellow powder,

which sinters when poured over with water and then easily goes into solution. The weak

Acidified solution makes a good tanning extract. Also, the product is used as a reservation agent for animal fibers against staining with nouns dyes and as a precipitant for basic dyes suitable.

The 3 "-aminobenzene-i" -sulfonyl-3'-aminobenzene-i'-sulfonylaniline-4-sulfonic acid can be done by others according to the same construction principle

ίο represented dinuclear or polynuclear amidoarylsulfonamidoarylsulfonic acids be replaced, the individual chain links belonging to the benzene, naphthalene or diphenyl series and, for example, can also be substituted as desired by halogen or alkyl groups. Instead of this one for the shortcut the chains used ι ^ -Dichlorbenzol ^ -ö-disulfochlorids one can also benzene-i 3-disulfochloride, toluene disulfochloride, other halogen-substituted benzene disulfochlorides, naphthalene or diphenyl disulfochlorides or aromatic ones and aliphatic dicarboxylic acid chlorides including phosgene.

Mixtures of differently constituted amidoarylsulfonamidoarylsulfonic acids can also be used can be used for the stifling reaction, which also improves the properties the end products the intended use

3 <> purposes can be largely influenced accordingly are.

Example 2

206 parts of the mono-3 '· 4'-dichlorobenzoli'-sulfonyl-2 6-tolylene-4-sulfonic acid (can be produced by condensation of 6-oxalylamido-2-toluidine-4-sulfonic acid with 3 · 4-dichlorobenzene-i-sulfochloride and saponification of the oxalyl group) are mixed with about 2500 parts of water with the addition of 27 parts Soda brought into neutral solution. In the solution mixed with 42 parts of chalk one carries at ordinary temperature 86 parts of benzol · 3-disulphochloride, which was previously added a fine paste with water. The mixture is left at the usual Stir temperature until only traces of diazotized substance remain in the reaction mixture available. The mixture is then heated to 50 ° to 60 ° for a few hours, acidified with crude hydrochloric acid and the condensation product is precipitated with a conc. Calcium chloride solution. The chewy syrup after pouring and pressing the broth in the cold is brought into solution 2 to 3 times with about 900 parts of warm water at 60 ° and with the amount of conc. Calcium chloride solution precipitated again and the lime salt obtained in this way by double conversion with sodium oxalate or ammonium oxalate into the associated sodium or ammonium salt converted. These salts of the condensation product of the formula

Cl- <
Cl

J. , _ J '^ 95

SO, - NH- ⁷ '-NH-SO ₂ - ^{7 X} -SO ₂ -NH- ⁷ -NH-SO ₂ - _x ^) - Cl

Cl

SO ₃ H

when dried, they form colorless powders that easily dissolve in water. The weakly acidified Solutions are excellent tannin extracts, which the animal skin prepared in the usual way in one able to transfer extremely lightfast white leather.

Example 3

351 parts of mono - 3 '- nitrobenzoyl - 2 · 6-toluenediamine.-4-sulfonic acid (Can be produced, for example, by condensation of 6-oxalylamido-2-toluidine-4-sulfonic acid with 3-nitrobenzoyl chloride and subsequent saponification of the oxalylamido group) are with about 2000 parts of water and the equivalent amount of sodium hydroxide solution were brought into solution while hot. It is cooled to about 25 °, 80 parts of chalk and one with a little cold water are used well-ground paste of 173 parts of benzene-1 · 3-disulfochloride and leaves at

SO ₃ H ioo

Stir at a comfortable temperature until only traces of diazotizable substance can be detected. The mixture is then slowly heated to 50 to 60 °, held at this temperature for a few hours and the reaction mixture is made acidic to the Congo with crude hydrochloric acid. The condensation product precipitates in a syrupy form and can be obtained after cooling by pouring off and pressing the mother liquor in the form of a tough, coherent, brownish colored cake. This item ships with about 2000 parts of water hot again brought into solution and the solution obtained mulled well in a weak acidified with hydrochloric acid, about 90 ⁰ hot slurry of 400 parts of iron powder in 2000 parts of water added. When the reduction is complete, it is made alkaline with sodium hydroxide solution, the broth is suctioned off from the iron sludge and allowed to form a solution of with stirring

Excess raw hydrochloric acid in cold hive as a granular powder the reduction water flow out, with a good result of the formula

SO ₂ -NH

-NH-CO

NH.,

SO ₈ H CH,

SO ₂ -NH- ⁷ VNH- CO- /

NH,

SO ₃ H

ruled out. The connection is difficult to break in cold, easy in warm soda Water and, when diazotized, gives a weakly colored diazo compound which is sparingly soluble in cold water and which, with 2-naphthol-3 · Sodium 6-disulfonate couples to an orange-red colored azo dye.

211 parts of the pure diamino compound are dissolved neutrally with about 2500 parts of water and the necessary amount of sodium hydroxide solution. In the mixed with 40 parts of chalk, about 75 ° warm, well stirred solution is allowed 148 parts of 3 · 4-dichlorobenzene-i-sulfochloride flow in. The reaction starts immediately, and after a short time the condensation product begins from the formula

CH,

SO ₂ -NH-

NH-SO ₂ - <

Cl

> - Cl

NH-CO- /

SO ₃ H CH ₃

SO ₂ -NH- ^N -NH

SO ₃ H

to be excreted as a viscous mass. It still leaves some time at 80 to 90 ⁰ to stir, making brute hydrochloric acid mineral acid and cools. That then excreted from the solution as a coherent viscous mass

- Sodium lime salt of the condensation product is in the manner described by multiple Reprecipitation converted into the lime salt, which is sparingly soluble and can be freed from neutral salts by washing with warm water. Wins from the lime salt by reacting with the necessary amount of ammonium oxalate, the ammonium salt, which is readily soluble in water, is the excellent one Has tannic properties.

Example 4

387 parts of mono-3'-nitrobenzene-i'-sulfonyl-2 6-toluenediamine-4-sulfonic acid (her-

CO -

NH-SO ₂ - <

Cl

adjustable, for example, by condensation of 6-oxalylamino-2-toluidine-4-sulfonic acid with 3-nitrobenzenesulfochloride and subsequent saponification of the oxalylamino group) are dissolved with about 3500 parts of water and the equivalent amount of sodium hydroxide solution. 90 parts of chalk and 186 parts into the cooled to about 20 ^0, well mulled solution benzene-1 x 3 disulfochloride that have been previously wed with cold water to a homogeneous paste, registered. The mixture is left to stir for about 12 hours at normal temperature and then slowly brought to 50 to 60 °, at which temperature is then held for several hours. The resulting solution, which may only contain traces of diazotizable substance, is adjusted to mineral acid with crude hydrochloric acid and with that for the precipitation of the condensation product

necessary amount of a conc. Calcium chloride solution added. The syrupy substance is freed from the broth as much as possible by pouring it off and pressing it cold. She is brought to about 3000 parts water hot again in solution and left to stand at 90 ⁰ in a well-mulled, slightly acidified slurry of 400 parts of iron powder in 3000 parts of water into running. When the reduction is complete, the mixture is made alkaline, the iron sludge is suctioned off from the broth and the excess hydrochloric acid is poured into it while stirring. The amino compound of the formula

.SO, - NH- '' ^V NH- SO, -

\ /
SO ₃ H
CH,

SO, - NH-i V NH - SO ₂ - '

NHo

NH,

precipitates in granular form and can be isolated by suction. It forms dried a colorless powder that is difficult to dissolve in cold water and more easily soluble in hot water; absorbs the right amount of nitrite. The tetrazo compound, which in the diazotization precipitates in the form of pale yellow flakes, forms, with 2-naphthol-3 · 6-disulfonic acid Sodium combined in a soda-alkaline solution, an orange-red colored azo dye.

229 parts of diamino compound are mixed with about 3000 parts of water and the equivalent Amount of soda brought into neutral solution.

CH,

A resolution of 150 parts of crystalline is used. Sodium acetate added and the mixture at about 40 ⁰ to the agitator 90 parts of benzoyl chloride are added dropwise. Then the free acetic acid in the solution is blunted with soda and the sodium salt of the condensation product is precipitated with the necessary amount of a saturated saline solution. When the reaction mixture cools, the precipitated syrupy substance solidifies into a viscous paste, from which the broth can be poured off and pressed off. The product obtained can be cleaned by dissolving it again in hot water and precipitating it with table salt. The drug to which the formula

SO,-

SOo

when dried is a pale yellowish powder, which easily turns into cold and warm water dissolves and shows good tannic properties.

Example 5

237 parts of the disodium salt of 3'-aminobenzenesulfonyl - 2 - amino - 6 - oxalylamino-i-to-

NH- S0 _L -NH NH • SO, - ' NH -CO- r ' CH
I. \ N / A N / A 3 \ NH SO ₃ ■ so ₂ - ( NH -C0- <'
\

ΙιΐΰΙ-4-sulfonic acid (can be produced by condensation of 6-oxalylamino-2-toluidine-4-sulfonic acid with 3-nitrobenzenesulfochloride and Reduction of the nitro group) are dissolved in about 2500 parts of water. In the ordinary At the temperature well stirred solution, 40 parts of chalk and 75 parts of benzene-i · 3-disulfochloride are entered, the

one has previously ground to a homogeneous paste with cold water. One lets Stir for a number of hours until the condensation product precipitates and in there is no more nitrite-absorbing substance in the broth. The mixture is then acidified with crude hydrochloric acid and sucks off the granular substance. The paste, which is the condensation product of the formula

CH,

SO ₂ -NH- ^{7 X} -NH-CO-COOH

SO ₂ -NH--

SO ₀ -NH-;

contains as Kalknatriumsalz is heated with 1,500 parts by volume of an approximately io ° / ₀ hydrochloric acid ι hour at reflux with stirring for cooking. When the sucked through solution cools, the free diamino compound precipitates and can be isolated. They are redissolved in neutral solution with about 2000 parts of water and the necessary amount of soda, after cooling, about 40 parts of chalk and 135 parts of 3 · 4-dichlorobenzene-i-sulfochloride are added and SO ₃ H is left

CH ₁

SO ₉ -NH -NH-CO-COOH

SO ₃ H

Stir at normal temperature until no more diazotizable substances can be detected leaves. The mixture is then warmed to 5 ° to 60 °, acidified with crude hydrochloric acid and the reaction product, which is granular in the cold, is sucked off away. The lime-soda-salt mixture obtained in this way is converted into the sodium salt in the usual way convicted. The resulting calcium oxalate is sucked off in the heat, and the condensation product is obtained from the formula

CH,

SO ₉ -NH- '''VNH-SO ₂ -';

Cl

SO ₂ -NH- <

SO ₃ Na
\ CH ₃

SO ₂ -NH- / N-NH · SO ₂ ~ <{ N-Cl

Ci

S O, Na

dissolved to a pale yellow colored syrup, which after adding small amounts of organic Acid is an excellent tanning extract.

Example 6

566 parts (3'-aminobenzenesulfonyl) 6-amino- (3 "x 4" -dichlorobenzenesulfonyl) -2-amino-i-toluene-4-sulfonic acid from the formula

NH.,

( N

-SO ₈

- NH SO, - \

egg

SO, H

(can be prepared, for example, by reacting 3 · 4-dichlorobenzene-i-sulfochloride with o-Oxalylamino ^ -toluene ^ -sulfonic acid, saponification the oxalylamino group, condensation of the saponification product with 3-nitrobenzenesulfochloride and reduction of the nitro group) are mixed with about 4000 parts of water with the addition of the necessary amount of sodium hydroxide solution brought into neutral solution. About 70 parts of chalk and 159 parts of benzoli are added to the solution, which has been cooled to about 20 ° · 3-disulfochloride entered in the form of an aqueous paste. Leave for about 12 hours stir at normal temperature, then heat slowly to 50 to 60 ° and keep at this temperature for a few hours. As soon as only traces of diazotizable substance can be detected, the broth is acidified with raw hydrochloric acid, wherein the condensation product in oily, solidifying when the mixture cools Form fails. The substance has the same chemical composition as the crude product shown in Example 5 and is processed in a similar way to the sodium or ammonium salt.

SO, —NH-

Example 7

566 parts (3'-aminobenzenesulfonyl) 6-amino- (3 "· 4" -dichlorobenzenesulfonyl) 2-amino-i-toluene-4-sulfonic acid are dissolved with about 4000 parts of water with the addition of the equivalent amount of sodium hydroxide solution. The solution is cooled to about 20 ° and 80 parts of chalk and 264 parts of sulfobenzide disulfochloride (Beilstein, "Handbuch derorganischen Chemie", 4th edition, vol. 11, p. 241) are added, which are previously added with a little cold water a homogeneous, fine-grained paste as possible. The mixture is left for 12 hours at about ordinary temperature, mix well and then the temperature is raised gradually over a further 12 hours 60 to 70 ⁰ and finally at about 90 ^0th If only traces of diazotizable substance can be detected, the broth is made Congo acidic with raw hydrochloric acid, the condensation product precipitating as a viscous syrup. The cooled broth is poured off from the solidified paste and pressed and the mixture of sodium and calcium salt of the condensation product is converted into the ammonium salt of the formula in the manner described

^ ti., ^y

SO ₂ -NH- -NH-SO ₂ -

Cl

SO,

SO ₂ - NH- <

convicted. The product forms a very viscous one in about 25% solution yellow syrup, from which an almost colorless powder can be obtained when it dries up, which easily dissolves again with sintering in warm water. The weak with organic Acid-acidified syrup is an excellent tanning extract.

SO ₃ NH ₁

CH ₃

SO ₉ -NH- ^X -NH- SO, -. '

Cl

Cl

SO, NH _d

Example 8

566 parts (3 '- aminobenzenesulfonyl) -

6 - amino - (3 "x 4" - dichlorobenzenesulfonyl) 2-amino-i-toluene-4-sulfonic acid become neutral in solution with about 4000 parts of water with the addition of the necessary amount of sodium hydroxide solution brought. The solution is cooled to about 20 ° and 80 parts of chalk are worn a fine prepared from 204 parts of naphthalene-1 · 5-disulfochloride in a little cold water ground paste. The mixture is left to stir for about 12 hours at normal temperature, then warmed up to about 60 ° within a further 12 hours and finally a few more Hours at 90 to 95 °. If only traces of diazotizable substance can be detected are, the condensation product falls in the heat with crude hydrochloric acid as light colored syrup, cool the mixture and remove the broth by draining and Squeeze the crumbly grainy in the cold

nascent mass. From this, the readily soluble Am is made in the manner described monium salt of the condensation product. This ammonium salt of the formula

'SO ₂ -NH-NH-SO ₂ - <

) -Cl Cl

SO _n NH ₁

CH ₃

SO ₂ -NH-

forms a viscous one in about 25% solution yellowish syrup, from which you can easily turn it back into an almost colorless syrup by drying it with cold and warm water Solution to be brought powder can win.

The syrup, weakly acidified with organic acids, makes an excellent one Tanning extract. You get a very similar product if you look at the in the example described condensation the naphthalene · 5-disulfochloride about by the homologous Replaced naphthalene-2 · 6-disulfochloride.

Example 9

566 parts (3 '- aminobenzenesulfonyl) 6-amino -. (3 "· 4" - dichlorobenzenesulfonyl) -2-amino-i-toluene-4-sulfonic acid are brought into neutral solution with about 4000 parts of water with the addition of the necessary amount of sodium hydroxide solution . In this solution is passed to the agitator at about 40 ⁰ in the excess phosgene to give ensures by dropwise addition of dilute sodium hydroxide solution to it that the

ι- NH

SO ₃ NH ₁ VCl Cl

Broth always reacts slightly alkaline. If no or only very small amounts diazotizable substance are present, the sodium hydroxide supply is shut off and phosgene is introduced further the reaction mixture is minerally acidic. The phosgenation product, which is first has deposited in the form of a syrup from the acidic solution, increases when it cools the reaction mass becomes friable. The clear broth is removed by pouring it off and pressing off the paste and bringing it into place by adding about 3000 parts. Water hot in solution. By adding the necessary amount of conc. Calcium chloride solution is used to precipitate the condensation product in the form a mixture of its lime and sodium salt and carries out this salt mixture repeatedly precipitated with calcium chloride solution into the pure calcium salt. The well pressed lime salt is then used in as described in the ammonium salt of the formula

CH.,

SO ₂ - NH - NH-S O ₂ - <

_ rl

CO

S 0., NH ₁

Cl

SO, - NH - NH - SO., -

Cl

SO ₃ NH ₄

convicted. By evaporating the syrup obtained in this way, the body can be used as a Obtain weakly colored powder, which can easily be brought back into solution with water and good tanning effect in solution weakly acidified with organic acids.

shows. In the course of the process, for example, the phosgene can be passed through Replace oxalyl chloride or another aliphatic dicarboxylic acid chloride without the The tannic properties of the products obtained change significantly.

Example io

566 parts (3 '- aminobenzenesulfonyl) 6 - amino - (3 "x 4" - dichlorobenzenesulfonyl) ^ -amino-i-toluene- ^ sulfonic acid are brought into solution with about 4000 parts of water and the equivalent amount of sodium hydroxide solution. One contributes to the well-mixed solution

20 ° 80 parts of chalk and 153 parts of isophthalyl chloride and, by occasionally adding more soda solution, ensures that the reaction is always neutral to slightly alkaline remain. The condensation product begins to turn syrupy after a number of hours to be excreted at the bottom of the vessel. If only small amounts of diazotizable substance can be detected, acid is also used Hydrochloric acid and pour the mother liquor from the viscous paste. The sodium lime salt obtained is in the manner described in the lime salt, and this becomes the ammonium salt of the constitution

CH,

SO., —NH -NH-SO ₂ - /

CO NH-

CO-NH Cl

SO ₃ NH ₄ CH,

SO ₀ -NH- / ^X -NH- SO., - <

Cl

SO ₃ NH ₄

transferred that in about 25% aqueous Solution forms a thin colored syrup. You can do this by evaporation Obtain the product as a colorless powder that easily dissolves in cold and warm water again solves. The solution of the product is weakly acidified with organic acid well usable as tanning extract.

_{In Examples 2 to 10, monoaminoarylacidylamidoaryl derivatives (acidyl = SO 2} or CO) obtained from the 2 · 6-toluylenediamine-4-sulfonic acid were chosen as starting materials for the reactions described. For these linkage reactions, of course, you can also use preparations of similar structure from other diaminosulfonic acids of the benzene series, such as t 3-phenylenediamine-4-sulfonic acid and 5-sulfonic acid, 2 4-tolylenediamine-5- and -6-sulfonic acid, the 1 4-phenylenediamine-2-sulfonic acid and others, as well as mixtures

use such preparations and also receives condensation products, for example as tanning agents or reservation agents or precipitants for basic dyes Can be used.

Example 11

654 parts of bis (3-amino-benzene-i-sulfonyl) benzidine-mm-disulfonic acid (Patent 565,461, Example 6) are brought water and about 100 parts of chalk in solution at about 70 ⁰ with 6000Teilen. 65 parts of chalk are added to the well-stirred solution and 270 parts of 3 · 4-dichlorobenzene sulfochloride are added dropwise from the separating funnel. It is then kept at 70 to 80 ° for about ι hour and finally at 90 to 100 for a short time °. The reaction mixture is acidified with hydrochloric acid and cooled. The mono-i · 2-dichlorobenzene-4-sulfonyl-bis- (3'-aminobenzene-i'-sulfonyl) -benzidine-mm-disulfonic acid of the form]

Cl

Cl -.

NH-

SO, H

SO ₂ -NH- <) -NH-

NH ₁

Claims (1)

IO which arises here fairly uniformly, separates in the form of a firm, viscous paste ^ -a / n Bottom of the vessel and can be poured through and pressed from the anha | Broth to be freed. The product gets hot with about 4000 'of water and the necessary amount of soda dissolved and the neutral solution sucked through at ordinary temperature with 60 parts of chalk and one of 137.5 parts Cl Benzene-1 · 3-disulfochloride was mixed with a paste prepared by grinding with cold water. The stirred reaction mixture begins to become thick after some time, so that you have to go to about 35 to 40 ⁰ , the doughy mass going back into solution. If a sample shows that no more nitrite is being absorbed, it is acidified with hydrochloric acid. The condensation product of the formula Cl- / VS0 «-NH- < SO ₂ -N H- < Cl SO., - NH V-SOo-NH- / comes out in a syrupy form and solidifies into one when the broth cools down solid coherent mass. The broth is poured off and the well squeezed Paste of the lime-sodium-salt mixture converted into the ammonium salt in the manner described several times. This _{4 <)} returns with 3 times the amount of W ater ⁷ -a pale yellowish, rather liquid syrup which after weak acidification constitutes an excellent Gerbextrakt. The bis (3-aminobenzene-i-sulfonyl) -mm-disulfonic acid can, for example, by the bis- (3-aminobenzene-i-sulfonyl) -tolidine-mmdisulfonic acid or the bis- (3-aminobenzenesulfonyl) -diaminostilbenedisulfonic acid or analogues Diphenyl derivatives are replaced with other bridges between the two aryl nuclei. A bis (3-aminobenzene-1-sulfonyl) -phenylenediamine or toluenediamine sulfonic acid can also be used as the starting material. In all cases, preparations are created that are characterized by their reserve power for animal fibers and by their tannic properties. SO _:! H SO., H > -NH-SO, - SO ₃ H VNH-SO., " SO ₃ H P, \ T E N T A N S P R U CII: A process for preparing amide-like condensation products of aromatic sulfonic acids, characterized in that aromatic disulfone or dicarboxylic acid chlorides, aliphatic dicarboxylic acid chlorides or phosgene both sides group-containing aqueous solution with neutralized sulfonic acid i _O o Aminoarylacidylamidoarylverbindungen (Acidyl = - SO ₂ - and / or - CO -), which still contain an acidylatable amino group, reacts, any nitro groups or non-aromatically acylated amino groups present in the reaction products are reduced or exposed and the free amino groups thus formed are acylated in aqueous solution with neutralized arylsulphon no or carboxylic acid chlorides, the resulting products should contain at least four sulfiniido groups and at least two sulfonic acid groups.